Parasiticidal preparations



- drone-1,4 and its melting Patented Mar. 19, 1946 FFEZ ramsmcmu. rnnrana'rrons. .Elbert 0. ma, Passaic, NJ; assignmto United States Rubber-Company, New York, N.

corporation of New Jersey No Drawing.

This invention relates to new and useful improvements in parasiticidal preparations, more particularly to germicides, that is, fungicides and baetericides, and to preparations for repelling insects, including larvae, arachnids and acarids. The invention further relates to methods of, protecting Organic materials subject to attack by low orders of organisms, as the 'of seed, and the mildewprooflng of fabrics and other material.

I have found that z-chioronaphthoquinhydrone-1,4 is eflective for destroying or checking the growth of fungi and bacteria and repelling insects. The 2 chloronaphthoquinhydrone 1,4, which is believed to be a new compound, may be prepared by reacting equimolar' proportions of 2-chloronaphthoquinone-1,4 and z-chloronaph thalenediol 1,4. The z-chloronaphthoquinone- 1,4 is a pale yellow solid of 102-117 C. This compound and method of preparation are described in Beilsteins "Handbuch der Organischen Chemie," (4th Ed.) The 2 chloronaphthalenediol 1,4 may-be prepared from the-z-chloronaphthoquinone-1,4 by reduction, as by treating an aqueous suspension of the 2-chloronaphthoquinone-1,4 with stannous chloride. The 2-chloronaphth'ahaving a melting point Application September-.16, 1944, sol-nominees:

14Claims. 01. 167-82) used as a seed protectant and to protect plants.

- including plant parts, or soil from organisms harmful to seeds and plants. It may also be applied to prevent or retard fungus growth and the formation of mildew. for example, on organic materiaL'such as rope. wood, fur, hair, feathers,

cotton, wool, leather. rubber, rubberized or synthetic resin coated fabric, and the like. The

vol. 7, P ge 729 lenedi0l-1,4 is a white solid of melting point 138-,

140 C. The 2 chloronaphthoquinhydrone 1,4

may be-prepared by mixing equimolecular quantities of 2-chloronaphthoquinone-L4 and 2-chloronaphthalenediol-1,4 and preferably warming suiiiciently to complete or hasten completion of the reaction, The reaction is complete when the reactants have-been converted to a purple solid. The reaction may be prepared if desired-in the presence of a solvent or diluent. For example, 2.5 parts of 2-chloronaphthalenediol-1,4 and 2.4 parts of 2-chloronaphthoquinone-L4 (parts by weight) may be dissolved together in acetone and then evaporated to dryness on a steam bath. The

resultant 2-chloronaphthoquinhydrone-1,4 is a purple solid having a melting point of 142-143 C. The color of the 2-chloronaphtho'quinhypoint are ample eviis a quinhydrone and The structure of the dence that the material not a physical mixture.

. 2-chloronaphthoquinhydron -1,4, in accordance with the accepted usage in designating quinhydrones generally, may be represented as follows:

- n i I The 2-chloronaphthoquinhydrone-1,4 may be 0 product of chlorinated kerosene with benzene).

E'mmple I Pea s eed variety Perfection were tumbled with various proportions of 2-chloronaphthoquinhydrone-1,4 in dust form. The seeds were then planted in soil known to be infected with a number of organisms including Pzlthium ultimum. The effectiveness of the compound as a fungicide was determined by comparing the numbers of seeds which germinated and developed into healthy plants from equal numbers of treated and untreated seeds planted under the same conditions. Observations were made at the end of 10 dayson the seeds treated with various dosages of the z-chioronaphthoquinhydrone-1,4. The results are shown in the following table Percent germination after 10 days Dosage of 9-chloronaphthoquinhydrone h4 in percent of seed weight Temd treated Example II fungi using the slidetechnique described by S. E. A. McCallan et al., Contributions of Boyce- Y Thompsoninstituted 4, 233 (1932); 9, 249 (1938) 10, 329 (1939); 12, 431 (1942 is given in the following table: In all cases the concentration of the 2-chloronaphthoquinhydrone-L4 was one part per million suspended in water containing .00625% Nacconal NR (a proprietary dispersing agent which is the sulphonated condensation Percent ungorminatodepores Iunzus treated Treated tr a ted Example Ii! This case illustrates the eflective'nes s of '2- chloronaphthoquinhydrone-1,4 as a bactericide. by weight 01' finely divided 2-chloronaphthoquinhydrone-L4 was suspendedflinwater which contained 2% or Emulphor' EL (believedjto be the reaction product or fatty acid or fatty acid ester with ethylene oxide) as a dispersin agent. -Pieces of diced carrot were immersed in this suspension and allowed to stand at room temperature. No growth of naturally occurrin bacteria was observed after 30 days. On the other hand, pieces of diced carrot treated in a .similar'way with a- 2% solution 01 Emulphor EL in water, which solution did not contain a germicide, became heavily overgrown with naturally occurring bacteria within the same period oi time. V v

'Exampla IV L The insect repellent properties of 2-chloronaphthoquinhydrone-"Li are shown by the following test: .5 part by weight or 2-chloronaph- 'thoquinhydrone-lA' in finely ground. form was disp rsed in200 parts of; water containing .001- part by weight of Nacconal NR. Two young bean plants with the ilrst'true leaves fully expanded were sprayed with this aqueous suspension, of 2- chloronaphthoquinhydrone-ln in amount sufflcient to wet the entire leaf surfaces. The plants were then: placed in, an insect cage and infested with ten Merdcanf bean beetle larvae. Two other young bean plants were sprayed with asolution comprising .001 part of Nacconal NR in water but not containing any other added chemical, and were similarly infested. with Mexican beanv beetle larvae at the 'same time. After six days it was observed that only to 1 5% or the leaves or the treated plants had beeneaten, whereas the leaves or the control plants was only. with the aqueous solution oi Nac'conal NRwere completely skeletonized.

Having thus described my invention, what 1 claim and desire to protect by Letters Patent is:

1. As at 'new hydrone-lA. I

2. An insect repellentcompositioncornprising a carrier and z-chloronaphthoquinhydrone-ln as m an active ingredient.

3. A fungicidal composition comprising a carrier and '2-chloronaphthoquinhydrone-L4 as an v active ingredient.

4'. Aiungicidal composition comprising a liquid carrier and 2-chlorcnaphthoquinhydrone-L4 as chemical,- 2-chloronaphthoquinan'a ctive ingredient. I

5. A germicidal preparation comprising an aqueous suspension of 2-chloronaphthoquinhych1oronaphthoquinhydrone-L4.

10. The method of destroying fungus which comprises subjecting said fungus to the action of 2-chloronaphthoquinhydrone-l,4.

ganic material which comprises treating =said organic material with 2-chloronaphthoquinhy--' drone-11,4. 4o 12. The method of combating insects which comprises applying drone-1,4 to the insect host. x

13. The method of combating fungi, bacteria'. and insects which comprises treating material liable to attack by said fungi, bacteria andinsects with 'a' composition containing '2-chloronaphthoquinhydrone-Li.

' 14. The method 7 n chloronaphthoquinhi drone-IA to loci't'o be proteoted against insects. I

ELBERT- C. LADD.

11.-The method of controlling mildew on or-' 2-chloronaphthoquinhywhich comprises applying 2 

